Method of forming MIS capacitor

ABSTRACT

An MIS capacitor with low leakage and high capacitance is disclosed. A layer of hemispherical grained polysilicon (HSG) is formed as a lower electrode. Prior to the dielectric formation, the hemispherical grained polysilicon layer may be optionally subjected to a nitridization or anneal process. A dielectric layer of aluminum oxide (Al 2 O 3 ), or a composite stack of interleaved layers of aluminum oxide and other metal oxide dielectric materials, is fabricated over the hemispherical grained polysilicon layer and after the optional nitridization or anneal process. The dielectric layer of aluminum oxide (Al 2 O 3 ) or the aluminum oxide composite stack may be optionally subjected to a post-deposition treatment to further increase the capacitance and decrease the leakage current. A metal nitride upper electrode is formed over the dielectric layer or the composite stack by a deposition technique or by atomic layer deposition.

This application is a division of U.S. application Ser. No. 10/145,993,filed May 16, 2002.

FIELD OF THE INVENTION

The present invention relates to the field of integrated circuits and,in particular, to a novel method of forming capacitor structures.

BACKGROUND OF THE INVENTION

A dynamic random access memory (DRAM) cell typically comprises a chargestorage capacitor coupled to an access device such as aMetal-Oxide-Semiconductor Field Effect Transistor (MOSFET). The MOSFETfunctions to apply or remove charge on the capacitor, thus affecting alogical state defined by the stored charge. The amount of charge storedon the capacitor is determined by the capacitance C=∈_(o) A/d, where ∈is the dielectric constant of the capacitor dielectric, ∈_(o) is thevacuum permittivity, A is the electrode (or storage node) area, and d isthe interelectrode spacing. The conditions of DRAM operation, such asoperating voltage, leakage rate and refresh rate, will in generalmandate that a certain minimum charge be stored by the capacitor.

In the continuing trend to higher memory capacity, the packing densityof storage cells must increase, yet each must maintain requiredcapacitance levels. This is a crucial demand of DRAM fabricationtechnologies if future generations of expanded memory array devices areto be successfully manufactured. Nevertheless, in the trend to highermemory capacity, the packing density of cell capacitors has increased atthe expense of available cell area. For example, the area allowed for asingle cell in a 64-Mbit DRAM is only about 1.4 μm². In such limitedareas, it is difficult to provide sufficient capacitance usingconventional stacked capacitor structures. Yet, design and operationalparameters determine the minimum charge required for reliable operationof the memory cell despite decreasing cell area.

Several techniques have been developed to increase the total chargecapacity or the capacitance of the cell capacitor without significantlyaffecting the cell area.

For example, new capacitor dielectric materials with high dielectricconstants have been introduced to replace conventional dielectricmaterials such as silicon nitride. This way, thin films of materialshaving a high dielectric constant, such as Ta₂O₅ (tantalum pentoxide),Barium Titanate (BT), Strontium Titanate (ST), Lead Zirconium Titanate(PZT), or Bismuth Strontium Titanate (BST), have been increasinglyutilized as the cell dielectric material of choice of DRAMs. Althoughthese materials have a high dielectric constant and low leakagecurrents, there are some technical difficulties associated with thesematerials.

One problem with incorporating these materials into current DRAM celldesigns is their chemical reactivity with the polycrystalline silicon(polysilicon or “poly”) that conventionally forms a capacitor electrodeof a metal-insulator-semiconductor (MIS) capacitor. Capacitors made ofpolysilicon-PZT/BST sandwiches undergo chemical and physical degradationwith thermal processing. During the chemical vapor deposition (CVD) ofPZT/BST, oxygen in the ambient tends to oxidize the electrode material.The oxide is undesirable because it has a much lower dielectric constantcompared to that of PZT/BST, and adds in series to the capacitance ofthe PZT/BST, thus drastically lowering the total capacitance of thecapacitor. Thus, even a thin native oxide layer present on the electroderesults in a large degradation in capacitance.

Accordingly, there is a need for a method of forming ametal-insulator-semiconductor (MIS) capacitor having increasedcapacitance per cell and low leakage, as well as a method of forming acapacitor structure that achieves high storage capacitance withoutincreasing the size of the capacitor. An MIS capacitor with increasedcapacitance and reduced leakage current is also needed.

BRIEF SUMMARY OF THE INVENTION

The present invention provides an MIS capacitor and a method of formingan MIS capacitor with low leakage and high capacitance.

The MIS capacitor of the present invention comprises a layer ofhemispherical grained polysilicon (HSG) as a lower capacitor electrode,which may be optionally nitridized or oxidized. A dielectric layercomprising aluminum oxide (Al₂O₃), or a dielectric composite stackcomprising one or more layers of Al₂O₃ interleaved with one or morelayers of other dielectric metal oxides, is provided over the layer ofhemispherical grained polysilicon (HSG). An upper electrode of a metalnitride layer is formed over the dielectric layer or the dielectriccomposite stack.

The present invention also provides a method of forming an MIS capacitorwith reduced leakage current and high capacitance. A layer ofhemispherical grained polysilicon (HSG) is formed as a lower electrode.After its formation and prior to the dielectric formation, the layer ofhemispherical grained polysilicon (HSG) may be subsequently subjected toa nitridization or an anneal process to passivate the HSG surface andimprove the cell capacitance and the leakage. A dielectric layercomprising aluminum oxide (Al₂O₃), or a dielectric composite stackcomprising a plurality of interleaved layers of Al₂O₃ and otherdielectric oxides, is formed over the layer of hemispherical grainedpolysilicon (HSG) by atomic layer deposition (ALD), for example. Thedielectric layer or the dielectric composite stack is optionallysubjected to a post-dielectric deposition treatment, for example, anitridization or an anneal treatment, to further reduce leakage andincrease the dielectric stability. An upper electrode of metal nitridematerial is formed over the dielectric layer or the dielectric compositestack by a deposition process or by an atomic layer deposition (ALD)method.

The foregoing and other advantages and features of the invention will bebetter understood from the following detailed description of theinvention, which is provided in connection with the accompanyingdrawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic cross-sectional view of a portion of a memory DRAMdevice, in which an MIS capacitor will be fabricated according to amethod of the present invention.

FIG. 2 is a schematic cross-sectional view of the FIG. 1 device at astage of processing subsequent to that shown in FIG. 1.

FIG. 3 is a schematic cross-sectional view of the FIG. 1 device at astage of processing subsequent to that shown in FIG. 2.

FIG. 4 is a schematic cross-sectional view of the FIG. 1 device at astage of processing subsequent to that shown in FIG. 3.

FIG. 5 is a schematic cross-sectional view of the FIG. 1 device at astage of processing subsequent to that shown in FIG. 4.

FIG. 6 is a schematic cross-sectional view of the FIG. 1 device at astage of processing subsequent to that shown in FIG. 5.

FIG. 7 is a schematic cross-sectional view of the FIG. 1 device at astage of processing subsequent to that shown in FIG. 6.

FIG. 8 is a schematic cross-sectional view of the FIG. 1 device at astage of processing subsequent to that shown in FIG. 7.

FIG. 9 is a schematic cross-sectional view of the FIG. 1 device at astage of processing subsequent to that shown in FIG. 8.

FIG. 10 is a schematic cross-sectional view of the FIG. 1 device at astage of processing subsequent to that shown in FIG. 9.

FIG. 11 is a schematic cross-sectional view of the FIG. 1 device at astage of processing subsequent to that shown in FIG. 10.

FIG. 12 is a schematic cross-sectional view of the FIG. 1 device at astage of processing subsequent to that shown in FIG. 11.

FIG. 13 is a schematic cross-sectional view of the FIG. 1 device at astage of processing subsequent to that shown in FIG. 11 and inaccordance with another embodiment of the present invention.

FIG. 14 is a schematic cross-sectional view of the FIG. 1 device at astage of processing subsequent to that shown in FIG. 11 and inaccordance with an embodiment of the present invention.

FIG. 15 is a schematic cross-sectional view of the FIG. 1 device at astage of processing subsequent to that shown in FIG. 11 and inaccordance with an embodiment of the present invention.

FIG. 16 is a schematic cross-sectional view of the FIG. 1 device at astage of processing subsequent to that shown in FIG. 11.

FIG. 17 is a schematic cross-sectional view of the FIG. 1 device at astage of processing subsequent to that shown in FIG. 12.

FIG. 18 is a schematic cross-sectional view of the FIG. 1 device at astage of processing subsequent to that shown in FIG. 17.

FIG. 19 is an illustration of a computer system having a memory devicewith an MIS capacitor constructed in accordance with the presentinvention.

FIG. 20 is a graph illustrating data measurements for the leakagecurrent and the capacitance of five MIS capacitors, of which three arefabricated according to embodiments of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

In the following detailed description, reference is made to variousspecific embodiments in which the invention may be practiced. Theseembodiments are described with sufficient detail to enable those skilledin the art to practice the invention, and it is to be understood thatother embodiments may be employed, and that structural, logical, andelectrical changes may be made.

The term “substrate” used in the following description may include anysemiconductor-based structure that has a semiconductor surface.Structure must be understood to include silicon, silicon-on insulator(SOI), silicon-on sapphire (SOS), doped and undoped semiconductors,epitaxial layers of silicon supported by a base semiconductorfoundation, and other semiconductor structures. The semiconductor alsoneed not be silicon-based. The semiconductor could be silicon-germanium,germanium, or gallium arsenide. When reference is made to a substrate inthe following description, previous process steps may have been utilizedto form regions or junctions in or on the base semiconductor orfoundation.

The term “metal” is intended to include not only elemental metal, butmetal with other trace metals or in various alloyed combinations withother metals as known in the semiconductor art, as long as such alloyremains electrically conductive. Similarly, the term “aluminum oxide”includes not only elemental aluminum oxide, but aluminum oxide withother trace materials or in various alloyed combinations as known in thesemiconductor art, as long as such alloy or combination retains thephysical and electrical properties of aluminum oxide.

Referring now to the drawings, where like elements are designated bylike reference numerals, FIG. 1 depicts a memory cell construction for aDRAM at an intermediate stage of the fabrication, in which a pair ofmemory cells having respective access transistors are formed on asubstrate 12. The FIG. 1 structure includes the substrate 12 having awell 13, which is typically doped to a predetermined conductivity, forexample p-type or n-type depending on whether NMOS or PMOS transistorswill be formed therein. The structure further includes field oxideregions 14, conventional doped active areas 16 for use as source/drainregions, and a pair of gate stacks 30, all formed according towell-known semiconductor processing techniques. The gate stacks 30include a gate oxide layer 18, a conductive gate layer 20, such aspolysilicon or polysilicon covered by a silicide, nitride spacers 32 anda nitride cap 22.

Above the gate oxide region 18, the polysilicon gates 20, and theprotective nitride regions 22, 32, a first insulating layer 24 (FIG. 1)is disposed. Insulating layer 24 could be formed of silicon oxide,borophosphosilicate glass (BPSG), borosilicate glass (BSG), orphosphosilicate glass (PSG), among others.

Reference is now made to FIG. 2, which for simplicity illustrates only alateral portion, for example, the right side portion of FIG. 1. This isa region where a contact plug and an overlying MIS capacitor structure100 (FIG. 18) fabricated according to exemplary embodiments of thepresent invention will be formed. To create a contact opening 40 (FIG.3) into the substrate 12 through the first insulating layer 24, aphotoresist material 26 (FIG. 2) is deposited and patterned usingconventional photolithography steps. After patterning, an initialopening 27 (FIG. 2) is formed in the photoresist layer 26 for subsequentoxide etching. The first insulating layer 24 of FIG. 2 is then etched,to form a contact opening 40, and the photoresist layer 26 is removed,as shown in FIG. 3. The contact opening 40 extends to the source/drainregion 16 provided in the well 13 of the substrate 12.

Next, contact opening 40 (FIG. 3) is filled with a conductive material,such as doped polysilicon, that is planarized down to or near the planarsurface of the first insulating layer 24, to form a polysilicon plug orfiller 50, as illustrated in FIG. 4. The polysilicon plug 50 is thenanisotropically etched until its top surface is recessed below theplanar surface of the first insulating layer 24, so that a barrier layer52 (FIG. 5) can be deposited and planarized, as shown in FIG. 5. Thebarrier layer 52, preferably of titanium (Ti), is formed on thepolysilicon plug 50 by CVD, PVD, sputtering or evaporation, to athickness of about 60 to about 200 Angstroms. The titanium barrier layer52 will form titanium silicide (TiSi₂) during a later high temperatureanneal.

Although the present invention is described with reference to theformation of an MIS capacitor 100 (FIG. 18) over the polysilicon plug50, including the barrier layer 52, it must be understood that theexistence of the barrier layer 52 is optional, and that the presentinvention also applies to capacitors formed over polysilicon plugswithout protective barrier layer 52.

FIG. 6 illustrates the deposition of a second insulating layer 25, whichcould be, for example, a silicon oxide, borophosphosilicate glass(BPSG), borosilicate glass (BSG), phosphosilicate glass (PSG), ortetraethylortho silicate (TEOS). The second insulating layer 25 isdeposited over the barrier layer 52 and the first insulating layer 24.Again, using the same fabrication technique as that used for theformation of contact opening 40 (FIG. 3) through the first insulatinglayer 24, a capacitor opening 41 (FIG. 7) is formed through the secondinsulating layer 25.

Subsequent to the formation of capacitor opening 41 of FIG. 7, a layer60 of semiconductive material is formed inside the capacitor opening 41and over the upper surface of the insulating layer 25, as illustrated inFIG. 8. Layer 60 of semiconductive material may comprise hemisphericalgrained polysilicon (HSG), silica, silicon, germanium, or any alloy ofsilica or germanium. Preferably, layer 60 of semiconductive material isformed of hemispherical grained polysilicon (HSG). If HSG is employed,the layer 60 may be formed by first depositing a layer of in-situ dopedpolysilicon followed by a deposition of undoped HSG. Subsequent heatinginherent in wafer processing could effectively conductively dope theoverlying HSG layer. Alternatively, the HSG layer 60 may be provided byin-situ arsenic doping of an entire HSG layer, or by depositingamorphous silicon and then using a selective seed followed by anannealing process. The HSG layer 60 is in electrical contact with thepreviously formed conductive plug 50 over the active area 16. Althoughthe present invention will be described below with reference to layer 60of semiconductive material as to the HSG layer 60, it must be understoodthat this embodiment is only exemplary and the invention is not limitedto it.

Referring now to FIG. 9, the capacitor opening 41 of FIG. 8 is nextfilled with a photoresist material 61 by, for example, spin coating atroom temperature and then solidifying it. The photoresist material 61,which can be any photochemical resin used in the semiconductor industry,as well as the horizontal portions of the HSG layer 60 located above thesecond insulating layer 25, are then planarized by CMP down to or nearthe planar surface of the upper surface of the second insulating layer25 to form a photoresist plug 63 (FIG. 10). The photoresist plug 63 actsas a protective barrier for portions of the HSG layer 60 which contactthe vertical walls of the contact opening 41, as well as for thehorizontal portion of the HSG layer 60 which is situated above thepolysilicon plug 50.

Next, the chemically mechanically polished photoresist plug 63 (FIG. 10)is removed by using conventional techniques, such as ashing or plasmaetching, to form the structure of FIG. 11. Upon removal of thephotoresist plug 63, the HSG layer 60 may be optionally cleaned with adilute cleaning solution, for example, a dilute solution of hydrofluoricacid (HF) with a 10:1 volumetric ratio of water to 49% HF, to remove anyimpurities and/or material residue present on the HSG layer 60.

Subsequent to the removal of the photoresist plug 63 and of the optionalcleaning step described above, the HSG layer 60 may be further subjectedto an etching solution, for example, a hydrofluoric acid (HF) etchingsolution, to form an etched HSG layer 62, as illustrated in FIG. 11. Theetching solution removes any native oxide formed over the HSG layer 60and further enlarges the openings of the HSG grains and activates theHSG grains of the HSG layer 60. This way, the etched HSG layer 62 withactivated HSG grains allows the subsequently deposited dielectricmaterial to achieve good conformal properties with the etched HSG layer62 and better step coverage.

According to an embodiment of the present invention, the etched HSGlayer 62 (FIG. 11) may be optionally subjected to a nitridizing or anoxidizing ambient to densify the etched HSG layer 62 and, therefore, todecrease the leakage and increase the cell capacitance. The nitridizingor oxidizing ambient of the present invention also passivates thesurface of the etched HSG layer 62 to prevent the unwanted diffusion andreactions between the etched HSG layer 62 and the oxide material of thesubsequently deposited dielectric material. In this manner, thepassivated surface of the etched HSG layer 62, which is a result of thenitridizing or oxidizing ambient, prevents any ion permeation in theetched HSG layer 62 such as oxygen ions from the subsequently depositedaluminum oxide layer 70 (FIG. 12) into the etched HSG layer 62. Thepassivation of the etched HSG layer 62 also eliminates the need for hightemperature anneals which are typically required for the formation of aconventional oxide dielectric layer as part of a capacitor stack on anHSG layer.

As such, the etched HSG layer 62 may be subjected to a nitridizingambient, for example, a rapid thermal nitridation (RTN) process, aremote plasma nitridization (RPN) process, an in-situ remote RFnitridization, or a combination of these processes. If an RPN process isemployed, the substrate 12 may be placed in a reaction chamber and theetched HSG layer 62 may be subsequently exposed to a nitrogen-containingplasma formed from N₂ and H₂ within the reaction chamber. An exemplarynitrogen-containing plasma mixture comprises by volume from about 10% toabout 80% of N₂ and from about 20% to about 90% H₂, at a temperature offrom about 100° C. to about 800° C., more preferably of about 400° C. toabout 600° C. The nitrogen-containing plasma mixture may furthercomprise argon (Ar) or another inert gas, typically in a percentage ofabout 0.01% to about 40% argon or inert gas, by volume.

Alternatively, the etched HSG layer 62 may be subjected to an annealtreatment, such as an in-situ PH₃ anneal at about 750° C. and for about30 minutes. A nitrogen (N₂) or ammonia (NH₃) plasma anneal, or any othernitrogen source plasma anneal, may be also employed with or without aninert gas for annealing the etched HSG layer 62 to confer a betterinterface between the etched HSG layer 62 and the subsequently formedmetal oxide dielectric layer.

If a rapid thermal nitridization (RTN) process is used for passivatingthe surface of the etched HSG layer 62 and, consequently, for improvingthe cell capacitance and reducing the leakage, the rapid thermalnitridization (RTN) process may take place at temperatures ranging fromabout 600° C. to about 1200° C., more preferably between about 600° C.to about 800° C., for a time period ranging from about 5 seconds toabout 60 seconds, preferably from about 20 seconds to about 60 seconds.

In another embodiment of the present invention, the etched HSG layer 62may be subjected to an oxidizing ambient, for example, a remote plasmaoxidation (RPO) ambient using an oxygen (O₂) or ozone (O₃) source, withor without ultraviolet light. A wet oxidizing chemistry may be also usedto induce the passivation of the surface of the etched HSG layer 62.

According to yet another embodiment of the present invention, the etchedHSG layer 62 may be subjected to both an anneal treatment, such as anin-situ PH₃ anneal, and a rapid thermal nitridization (RTN) process. Forexample, the etched HSG layer 62 may be first subjected to an in-situPH₃ anneal at about 750° C. and for about 30 minutes followed by an RTNtreatment at about 800° C. for about 60 seconds. According to anotherembodiment of the present invention and to further improve thecapacitance and decrease the leakage, a cleaning step may be performedbefore the anneal treatment. For example, a dilute cleaning solutionsuch as a dilute hydrofluoric acid (HF) solution having a 10:1volumetric ratio of water to 49% HF may be used before the in-situ PH₃anneal.

According to yet another embodiment of the invention, a cleaning stepmay be performed after the PH₃ treatment and before the rapid thermalnitridization (RTN) process. For example, a dilute cleaning solutionsuch as a dilute hydrofluoric acid (HF) solution having a 10:1volumetric ratio of water to 49% HF may be used after the in-situ PH₃anneal and before the nitridization step outlined above. To furtherimprove the capacitance and decrease the leakage, the etched HSG layer62 may be also subjected to a first cleaning step before the PH₃treatment, and to a second cleaning step after the PH₃ treatment andbefore the RTN anneal. The first and second cleaning steps may employthe same or different cleaning solutions.

Referring now to FIG. 12, after the processing of the etched HSG layer62, a dielectric layer 70 is formed over the etched HSG layer 62 and thetop surface of the second insulating layer 25. According to a preferredembodiment of the invention, the dielectric layer 70 is formed ofaluminum oxide (Al₂O₃) material and reference to the dielectric layer 70will be made in this application as to the aluminum oxide (Al₂O₃) layer70. Aluminum oxide is preferred over other dielectric metal oxidematerials, such as tantalum oxide (Ta₂O₅), for example, because aluminumoxide is more stable than these dielectric oxides at high processingtemperatures. In addition, unlike the majority of dielectric oxidesincluding Ta₂O₅ which require oxidation anneal temperatures higher than700° C. and about several hours of oxidation, aluminum oxide structuresdo not require an oxidation anneal after Al₂O₃ deposition. As known inthe art, metal oxide dielectric films such as Ta₂O₅ films requireoxidation anneals after their deposition. The oxidation anneal alsoforms an oxynitride layer which grows at the HSG/Ta₂O₅ interface, forexample. Unfortunately, although the oxynitride layer formed at theHSG/Ta₂O₅ interface decreases the leakage current significantly, it alsoreduces the effective permittivity and, therefore, the overallcapacitance of the MIS structure. As aluminum oxide structures do notrequire an oxidation anneal after Al₂O₃ deposition, the formation of alow permittivity oxynitride layer at the HSG/Al₂O₃ dielectric interfaceis eliminated and the capacitance of the MIS structure is not affectednegatively.

The Al₂O₃ dielectric layer 70 (FIG. 12) may be formed by a depositiontechnique, for example chemical vapor deposition (CVD), metalorganicchemical vapor deposition (MOCVD) or sputtering, among others, to athickness of about 10 Angstroms to about 500 Angstroms, more preferablyof about 25 Angstroms to about 100 Angstroms.

In yet another exemplary embodiment of the present invention, the Al₂O₃dielectric layer 70 of FIG. 12 is formed by an atomic layer deposition(ALD) technique to further improve the quality of the dielectric film.According to this embodiment, a first species of aluminum precursor,such as an aluminum source precursor, for example trimethyl-aluminum(TMA), is first deposited over the surface of the etched HSG layer 62(FIG. 11) and the second insulating layer 25 as a first monolayer. Asecond species of oxygen precursor, which may be an oxygen (O₂), anozone (O₃) or water (H₂O) source, for example, is next applied over themonolayer of the first species of precursor. The second species ofprecursor reacts with the monolayer of the first species of precursor toform an aluminum oxide (Al₂O₃) layer.

Each of the Al₂O₃ layers of the first and second species of precursorsis provided on the surface of the etched HSG layer 62 and over the uppersurface of the second insulating layer 25 by first pulsing the firstspecies (also called first precursor gas) and then the second species(also called second precursor gas) into the region of the surface of theetched HSG layer 62 and of the second insulating layer 25. The sequenceof depositing the monolayers of the first and second species ofprecursors can be repeated cycle after cycle and as often as needed,until a desired thickness is reached for the Al₂O₃ dielectric layer 70.Between each of the precursor gas pulses, the process region isexhausted and a pulse of purge gas is injected. In any event, thethickness of the Al₂O₃ dielectric layer 70 formed by the ALD processoutlined above is in the range of about 10 Angstroms to about 100Angstroms, more preferably of about 25 Angstroms to about 50 Angstroms.

FIGS. 13–15 illustrate exemplary embodiments of the present invention,according to which at least one aluminum-containing interfacial layer isformed between the Al₂O₃ dielectric layer 70 and the etched HSG layer62, and/or between the Al₂O₃ dielectric layer 70 and the subsequentlyformed upper electrode. For example, FIG. 13 illustrates an interfacialAl—O—Si layer 72 formed at the etched HSG layer 62/Al₂O₃ dielectriclayer 70 interface. FIG. 14 illustrates an interfacial Al-metal-O—Nlayer 74 formed at the Al₂O₃ dielectric layer 70/upper electrodeinterface. FIG. 15 illustrates both an interfacial Al—O—Si layer 72 andan interfacial Al-metal-O—N layer 74 formed at the respective interfacesof the Al₂O₃ dielectric layer 70 with the etched HSG layer 62 and withthe upper electrode to be formed.

The incorporation of silicon atoms in the aluminum-containinginterfacial Al—O—Si layer 72 confers a smooth and continuous interfacebetween the polysilicon of the etched HSG layer 62 and the dielectricmaterial of the Al₂O₃ dielectric layer 70. Similarly, the incorporationof metal atoms in the aluminum-containing interfacial Al-metal-O—N layer74 also confers a smooth and continuous interface between the dielectricmaterial of the Al₂O₃ dielectric layer 70 and the conductive material ofthe metal nitride upper electrode.

The interfacial Al—O—Si layer 72 of FIGS. 13 and 15 may be formed to athickness of about 5 Angstroms to about 50 Angstroms, by a depositionprocess, for example chemical vapor deposition (CVD), using an aluminumsource, an oxygen source and a silicon source as precursors. Forexample, the Al—O—Si layer 72 may be formed using trimethyl-aluminum(TMA) as the aluminum source precursor, ozone (O₃) as the oxygen sourceprecursor, and silane as the silicon source precursor, at a temperatureof about 100° C. to about 800° C., more preferably of about 400° C.

According to a preferred embodiment of the invention, the interfacialAl—O—Si layer 72 of FIGS. 13 and 15 may be formed in-situ during theformation of the Al₂O₃ dielectric layer 70 of FIG. 12. For example, theinterfacial Al—O—Si layer 72 (FIGS. 13, 15) may be formed in-situ duringthe atomic layer deposition of the Al₂O₃ dielectric layer 70, using asimilar sequence of steps described above for the formation of the Al₂O₃dielectric layer 70. According to the ALD embodiment, a first species ofaluminum precursor, such as an aluminum source precursor, for exampletrimethyl-aluminum (TMA), is first deposited over the surface of theetched HSG layer 62 (FIG. 11) and the second insulating layer 25 as afirst monolayer. A second species of oxygen precursor, which may be anoxygen (O₂) or an ozone (O₃) source, or water (H₂O) for example, is nextapplied over the monolayer of the first species of precursor. The secondspecies of precursor reacts with the monolayer of the first species ofprecursor to form an aluminum oxide (Al₂O₃) layer. A third species ofsilicon precursor, which may be silane or a multiple-order silane suchas di-silane or tri-silane, is next applied over the monolayer of thefirst and second species of precursor to form an Al—O—Si layer. Thesequence of depositing the monolayers of the first, second and thirdspecies of precursors is repeated cycle after cycle and as often asneeded, until the thickness for the interfacial Al—O—Si layer 72 (FIGS.13, 15) is of about 5 Angstroms to about 50 Angstroms.

The interfacial Al-metal-O—N layer 74 of FIGS. 14 and 15 formed at theAl₂O₃ dielectric layer 70/upper electrode interface may be also formedto a thickness of about 5 Angstroms to about 50 Angstroms, by either adeposition technique or by atomic layer deposition. The metal componentof the interfacial Al-metal-O—N layer 74 is similar to the metalcomponent of the metal nitride material which will form the upperelectrode. For example, if the upper electrode to be formed comprisestitanium nitride (TiN) material, then the interfacial Al-metal-O—N layer74 is an interfacial Al—Ti—O—N layer 74. Similarly, if the upperelectrode to be formed comprises tungsten nitride (WNx) material, thenthe interfacial Al-metal-ON layer 74 is an interfacial Al—W—O—N layer74. Although, for simplicity, reference to the Al-metal-O—N layer 74will be made below as to the Al—Ti—O—N layer 74, it must be understoodthat the invention is not limited to this embodiment and the inventioncontemplates the formation of various interfacial Al-metal-O—N layers74, according to the metal of choice of the metal nitride upperelectrode to be formed.

According to one embodiment of the invention, the Al—Ti—O—N layer 74(FIGS. 14, 15) may be formed to a thickness of about 5 Angstroms toabout 100 Angstroms, by a deposition process, for example atomic layerdeposition (ALD), using an aluminum source, a titanium source, an oxygensource and a nitrogen source as precursors. For example, the Al—Ti—O—Nlayer 74 may be formed using trimethyl-aluminum (TMA) as the aluminumsource precursor, titanium tetrachloride (TiCl₄) as the titanium source,ozone (O₃) as the oxygen source precursor, and ammonia (NH₃) source asthe nitrogen source precursor, at a temperature of about 100° C. toabout 800° C., more preferably of about 400° C.

According to a preferred embodiment of the invention, the interfacialAl—Ti—O—N layer 74 of FIGS. 14 and 15 may be formed in-situ during theformation of the Al₂O₃ dielectric layer 70 (FIG. 12) and of theinterfacial Al—O—Si layer 72 (FIGS. 13, 15). For example, theinterfacial Al—Ti—O—N layer 74 (FIGS. 14, 15) may be formed in-situduring the atomic layer deposition of the Al₂O₃ dielectric layer 70 andof the Al—Ti—O—N layer 74, using a similar sequence of steps describedabove for the formation of the Al₂O₃ dielectric layer 70 (FIG. 12). Assuch, monolayers of aluminum, titanium, oxygen and nitrogen speciesprecursors, are sequentially deposited cycle after cycle and as often asneeded, until the thickness for the interfacial Al—Ti—O—N layer 74 ofFIGS. 14 and 15 is of about 5 Angstroms to about 100 Angstroms.

FIG. 16 illustrates yet another embodiment of the present invention,according to which a dielectric Al₂O₃ composite stack layer 80 is formedover the etched HSG layer 62 and the upper surface of the secondinsulating layer 25. The Al₂O₃ composite stack layer 80 may comprise oneor more layers of aluminum oxide interleaved with one or more layers ofother dielectric materials such as tantalum oxide, (Ta₂O₅), zirconiumoxide (ZrO₂), hafnium oxide (HfO), a hafnium-aluminum-oxygen alloy(Hf—Al—O), or a lanthanum-aluminum-oxygen alloy (La—Al—O), among others.

For example, the composite stack layer 80 may be an in-situ depositedcomposite stack of Al₂O₃/Ta₂O₄ (aluminum oxide/tantalum oxide), or anin-situ deposited composite stack of Al₂O₃/Ta₂O₅/Al₂O₃ (aluminumoxide/tantalum oxide/aluminum oxide), or a composite stack comprising aplurality of interleaved and alternating layers of Al₂O₃(aluminum oxide)and Ta₂O₅ (tantalum oxide). Since the permittivity of bulk Al₂O₃(aluminum oxide) is lower than that of Ta₂O₅ (tantalum oxide), theaddition of Ta₂O₅ (tantalum oxide) to a composite stack comprising Al₂O₃(aluminum oxide) significantly increases the overall permittivity of thecomposite stack. Also, since Al₂O₃ has a dielectric constant (of about9–12) lower than the dielectric constant of Ta₂O₅ (of about 18–45), theaddition of Ta₂O₅ further increases the total dielectric constant of theAl₂O₃/Ta₂O₅ (aluminum oxide/tantalum oxide) or Al₂O₃/Ta₂O₅/Al₂O₃(aluminum oxide/tantalum oxide/aluminum oxide) stacks and thus the totalcapacitance. In addition, a smooth HSG/Al₂O₃ interface is achievedwithout any need for an additional interfacial layer. In any event, thetotal thickness of the Al₂O₃ composite stack layer 80 is of about 10Angstroms to about 500 Angstroms, more preferably of about 25 Angstromsto about 100 Angstroms.

The Al₂O₃ composite stack layer 80 may be further formed as a pluralityof interleaved layers of Al₂O₃ and other dielectric oxides, for example,zirconium oxide (ZrO₂), hafnium oxide (HfO), a hafnium-aluminum-oxygenalloy (Hf—Al—O), or a lanthanum-aluminum-oxygen alloy (La—Al—O), amongothers. The Al₂O₃ composite stack layer 80 may be also formed as aplurality of interleaved layers of Al₂O₃ and a combination of dielectricmetal oxides, for example, a combination of any of zirconium oxide(ZrO₂), hafnium oxide (HfO), a hafnium-aluminum-oxygen alloy (Hf—Al—O),or a lanthanum-aluminum-oxygen alloy (La—Al—O), among others. In suchcases, each of the aluminum oxide and of the dielectric metal oxides maybe formed by either a deposition technique, for example chemical vapordeposition (CVD) or plasma enhanced chemical vapor deposition (PECVD),or by atomic layer deposition (ALD), the processing details of whichwere described above with reference to the formation of the Al₂O₃dielectric layer 70 of FIG. 12. Each of the above-mentioned layers orplurality of interleaved layers of the Al₂O₃ composite stack layer 80may be formed in-situ during the formation of the aluminum oxide layer,for example, via ALD.

Subsequent to the formation of the Al₂O₃ dielectric layer 70 (FIG. 12)or of the Al₂O₃ composite stack layer 80 (FIG. 16), the dielectricmaterial may be further subjected to a post-Al₂O₃ deposition treatmentto further increase the stack stability and the stack capacitancewithout degrading the leakage current. The post-Al₂O₃ depositiontreatment of the present invention replaces the conventionalpost-oxidation anneal, also known in the art as reoxidation, whichconventional dielectric oxides must undergo after their initialformation to significantly reduce the leakage current. As known in theart, dielectric oxides formed over a lower capacitor electrode haveoxygen (O₂) vacancies, the presence of which significantly affects theleakage current. To decrease the number of unwanted oxygen vacancies,the dielectric oxide is subjected to a reoxidation treatment which,although significantly decreasing the leakage current, also adverselyaffects the physical and electrical properties of the dielectric oxideand of the underlying polysilicon material, particularly as a result ofthe high oxidation temperatures. As described in more detail below withreference to FIG. 20, the formation of a 55 Angstroms Al₂O₃ dielectriclayer which undergoes a post-Al₂O₃ deposition confers acceptable leakagevalues without the conventional reoxidation treatment required fordielectric oxide materials.

Accordingly, as part of the post-Al₂O₃ deposition treatment forincreasing the stack stability and the stack capacitance withoutdegrading the leakage current, the Al₂O₃ dielectric layer 70 (FIG. 12)or the Al₂O₃ composite stack layer 80 (FIG. 16) may be subjected to amild surface nitridization process. This way, the dielectric layers 70,80 may be exposed to a nitridizing ambient under an RTN treatment fromabout 500° C. to about 900° C. for about 60 seconds. Alternatively, theAl₂O₃ dielectric layer 70 or the Al₂O₃ composite stack layer 80 may beexposed to a nitrogen-containing plasma formed from N₂ and H₂ within thereaction chamber. An exemplary nitrogen-containing plasma mixturecomprises by volume from about 10% to about 80% of N₂ and from about 20%to about 90% H₂, at a temperature of from about 100° C. to about 800°C., more preferably of about 400° C. to about 600° C. Thenitrogen-containing plasma mixture may further comprise argon (Ar) oranother inert gas, typically in a percentage of about 0.01% to about 40%argon or inert gas, by volume.

Referring now to FIG. 17, after the processing of the dielectric layeris completed, a metal nitride layer 90 is formed as an upper capacitorelectrode 90 to complete the formation of the MIS capacitor 100 (FIG.18). Although the completion of the formation of the MIS capacitor 100(FIG. 18) is explained below with reference to an upper capacitorelectrode formed over the Al₂O₃ dielectric layer 70 (FIG. 12), it mustbe understood that this embodiment is only exemplary. Accordingly, thepresent invention also contemplates the formation of an upper electrodeover other Al₂O₃ dielectric structures formed according to embodimentsof the present invention, for example the Al₂O₃ dielectric layer 70 withthe interfacial layers 72, 74 (FIGS. 13–15), or the Al₂O₃ compositestack layer 80 (FIG. 16).

As illustrated in FIG. 17, the metal nitride layer 90 is formed over theAl₂O₃ dielectric layer 70 of FIG. 12 to a thickness of about 10Angstroms to about 1,000 Angstroms, more preferably of about 50Angstroms to about 250 Angstroms. The metal nitride layer 90 (FIG. 17)may be formed, for example, of titanium nitride (TiN) material which isan extremely hard material that is almost chemically inert (although itdissolves readily in hydrofluoric acid) and has excellent conductiveproperties. Titanium nitride also has a high melting point (about 3000°C.), which makes it unaffected by high processing temperatures and bymost reagents.

According to an embodiment of the present invention, the titaniumnitride layer 90 may be formed by a chemical vapor deposition (CVD)process using a metal source and a nitrogen source as precursors, at atemperature of about 500° C. to about 800° C., more preferably of about600° C. For example, the titanium nitride layer 90 may be formed using anitrogen source, such as an ammonia (NH₃) source, and a titanium sourceprecursor containing chlorine (Cl), such as TiCl₄ (titaniumtetrachloride), (C₅H₅)₂TiCl₂ [bis(cyclopentadienyl)titanium dichloride]or (C₅H₅)TiCl₃ (cyclopentadienyltitanium trichloride), among others.Alternatively, the titanium nitride layer 90 may be formed by alow-temperature chemical vapor deposition (CVD) process by adding(CH₃)HNNH₂ (methylhydrazine) to a titanium source containing chlorine(Cl), for example TiCl₄ (titanium tetrachloride). A metalorganicprecursor such as TiN[CH₂(CH₃)₂]₄ (tetrakis diethylamino titanium orTDEAT) or Ti[N(CH₃)₂]₄ (tetrakis dimethylamino titanium or TDMAT) may bealso used with a nitrogen source precursor to form the titanium nitridelayer 90 of FIG. 17.

According to yet another embodiment of the present invention, thetitanium nitride layer 90 (FIG. 17) may be formed by an atomic layerdeposition (ALD) process. Because the ALD process takes place at lowtemperatures, the low ALD temperatures prevent the degradation of theAl₂O₃ dielectric layer 70 during the ALD processing steps. The low ALDtemperatures also prevent the formation of additional oxygen vacanciesin the aluminum oxide material, which typically occur as a result ofhigh processing temperatures.

If ALD processing is employed, a first species of precursor, which maybe a titanium source precursor containing chlorine (Cl), such as TiCl₄(titanium tetrachloride) for example, is first deposited over thesurface of the dielectric layer 70 (FIG. 12) as a first monolayer. Asecond species of precursor, which may be an ammonia (NH₃) source, forexample, is next applied over the monolayer of the first species ofprecursor. The second species of precursor reacts with the monolayer ofthe first species of precursor to form a titanium nitride (TiN) layer.Each of the TiN layers of the first and second species of precursors areprovided on the surface of the dielectric layer 70 by first pulsing thefirst species (also called first precursor gas) and then the secondspecies (also called second precursor gas) into the region of thesurface of the dielectric layer 70. The sequence of depositing themonolayers of the first and second species of precursors can be repeatedcycle after cycle and as often as needed, until a desired thickness isreached for the titanium nitride (TiN) layer 90. Between each of theprecursor gas pulses, the process region is exhausted and a pulse ofpurge gas is injected. The thickness of the titanium nitride layer 90formed by the ALD process outlined above is in the range of about 10Angstroms to about 250 Angstroms, more preferably of about 100 Angstromsto about 200 Angstroms.

According to another embodiment of the present invention, the metalnitride layer 90 is formed of boron-doped titanium nitride (TiBN)material having a boron doping concentration of from about 0.01% toabout 30% (atomic percentage). Incorporation of boron into a titaniumnitride (TiN) film may be achieved by exposing the titanium nitride filmto B₂H₆ at a temperature of from about 200° C. to about 600° C., at apressure of from about 1 Torr to about 20 Torr, and for a period of timeof about 10 seconds to about 60 minutes to convert the titanium nitridefilm to the boron-doped titanium nitride layer 90 (FIG. 17).Alternatively, the incorporation of boron into a titanium nitride (TiN)film may be achieved by exposing the titanium nitride film to B₂H₆ andfurther to ultraviolet (UV) light, at a temperature of from about 200°C. to about 600° C., at a pressure of from about 1 Torr to about 20Torr, and for a period of time of about 10 seconds to about 60 minutes.Any wavelength in the ultraviolet range may be used for exposing theB₂H₆ and further incorporating the boron into the titanium nitridematerial. The boron-doped titanium nitride layer 90 (FIG. 17) may bealso formed by a chemical vapor deposition (CVD) process using a TiCl₄(titanium tetrachloride) source precursor, a B₂H₆ boron source and anammonia (NH₃) source at a temperature of about 600° C. to about 800° C.

According to yet another embodiment of the present invention, the metalnitride layer 90 (FIG. 17) may be formed of tungsten nitride (WN_(x))material by a chemical vapor deposition (CVD) process using a tungstenmetal source and a nitrogen source as precursors. For example, thetungsten nitride layer 90 may be formed using a nitrogen source, such asan ammonia (NH₃) source, and a tungsten source precursor such astungsten hexafluoride (WF₆), at a temperature of about 300° C. to about500° C., more preferably of about 400° C.

According to yet another embodiment of the present invention, thetungsten nitride (WN_(x)) layer 90 (FIG. 17) may be formed by an atomiclayer deposition (ALD) process, as described above with reference to theformation of the ALD-formed titanium nitride (TiN) layer 90. For this, afirst species of precursor which may be a tungsten source precursorcontaining fluorine (F), such as tungsten hexafluoride (WF₆) forexample, is first deposited over the initial surface of the Al₂O₃dielectric layer 70 (FIG. 12) as a first monolayer. A second species ofprecursor, which may be a nitrogen (N₂) or an ammonia (NH₃) source, forexample, is next applied over the monolayer of the first species ofprecursor. The second species of precursor reacts with the monolayer ofthe first species of precursor to form a tungsten nitride (WN_(x))layer. Each of the WN_(v) layers of the first and second species ofprecursors is provided on the surface of the Al₂O₃ dielectric layer 70by first pulsing the first species and then the second species into theregion of the surface of the Al₂O₃ dielectric layer 70. As explainedabove, the sequence of depositing the monolayers of the first and secondspecies of precursors can be repeated cycle after cycle and as often asneeded, until a desired thickness is reached for the tungsten nitride(WN_(x)) layer 90. Preferably, the thickness of the tungsten nitridelayer 90 formed by the ALD process outlined above is in the range ofabout 10 Angstroms to about 250 Angstroms, more preferably of about 100Angstroms to about 200 Angstroms.

FIG. 18 illustrates the Al₂O₃ dielectric layer 70 and the metal nitridelayer 90 patterned by a dry etch process, for example, to complete theformation of the MIS capacitor 100 having an upper capacitor electrodeformed of metal nitride material. To this end, further well-knownprocessing steps to create a functional memory cell containing the MIScapacitor 100 may now be carried out.

A typical processor-based system 400 is illustrated in FIG. 19. Theprocessor-based system 400 includes a memory circuit 448, for example aDRAM memory, a SRAM memory, a Multi Chip Module (MCM), or a memorymodule containing one or more DRAM memory devices, at least one havingat least one MIS capacitor, such as the MIS capacitor 100 (FIG. 18)formed in accordance with the present invention. A processor system,which may be a computer system, generally comprises a central processingunit (CPU) 444, such as a microprocessor, a digital signal processor, orother programmable digital logic devices, which communicates with aninput/output (I/O) device 446 over a bus 452. The memory 448communicates with the CPU 444 for data exchange over bus 452 directly orthough a memory controller.

Examples of the implementation of the present invention will now bedescribed with reference to FIG. 20. In each of the five sets ofexperiments which will be described in more detail below, the leakagecurrents of one control capacitor and four MIS capacitors, of whichthree were fabricated according to methods of the present invention,were measured and recorded. More specifically, two sets of measurementswere run for a control capacitor and for one MIS capacitor formedaccording to embodiments of the prior art, and three sets ofmeasurements were run for three MIS capacitors fabricated according tovarious embodiments of the present invention. The data from each set ofmeasurements was recorded and illustrated in FIG. 20.

First Set of Experiments

Under a first set of experiments, an ONO capacitor was formed on asemiconductor wafer according to an embodiment of the prior art as acontrol capacitor. The control ONO capacitor was fabricated with a lowerelectrode of HSG of about 400 Angstroms thick, a silicon nitride (Si₃N₄)dielectric layer of about 50 Angstroms thick, and an upper electrode ofpolysilicon of about 200 Angstroms thick. The HSG lower electrode, theSi₃N₄ dielectric layer and the polysilicon upper electrode were formedby chemical vapor deposition (CVD) at a temperature of about 600° C.

A first group of measurements for the capacitance and leakage current ofthe control ONO capacitor described above was conducted from various dielocations across the wafer. The capacitance measurements were conductedat 1 kHz and zero (0) bias, and the corresponding leakage currentmeasurements were conducted at 1.5 V DC bias and at about 85° C. Thedistribution of the leakage current vs. capacitance measurements for thecontrol ONO capacitor was recorded as region A in FIG. 20. Asillustrated in FIG. 20, for capacitance values of about 22 to 29 fF/cellcorresponding to the region A, the leakage current values are within 0.5to 2.0 fA/cell.

Second Set of Experiments

Under a second set of experiments, a Ta₂Os MIS capacitor was formed on asemiconductor wafer according to another embodiment of the prior art.The Ta₂O₅ MIS capacitor was fabricated with a lower electrode of HSG ofabout 400 Angstroms thick, a Ta₂O₅ dielectric layer of about 40Angstroms thick, and an upper electrode of titanium nitride (TiN) ofabout 200 Angstroms thick. The HSG lower electrode was formed bychemical vapor deposition (CVD) at a temperature of about 600° C. TheTa₂O₅ dielectric layer was also formed by chemical vapor deposition(CVD) at a temperature of about 475° C., while the titanium nitrideupper electrode was formed by chemical vapor deposition (CVD) at atemperature of about 600° C.

A second group of measurements for the capacitance and leakage currentof the Ta₂O₅ MIS capacitor described above was conducted from variousdie locations across the wafer. The capacitance measurements wereconducted at 1 kHz and zero (0) bias, and the corresponding leakagecurrent measurements were conducted at 1.5 V DC bias and at about 85° C.The distribution of the leakage current vs. capacitance measurements forthe Ta₂O₅ MIS capacitor was recorded as region B in FIG. 20. Forcapacitance values of about 27 to 33 fF/cell corresponding to the regionB of FIG. 20, the leakage current values are within 0.5 to 3.0 fA/cell.

Third Set of Experiments

Under a third set of experiments, a first Al₂O₃ MIS capacitor was formedon a semiconductor wafer according to a first embodiment of the presentinvention. The first Al₂O₃ MIS capacitor was fabricated with a lowerelectrode of CVD hemispherical grained polysilicon of about 400Angstroms thick, an ALD Al₂O₃ dielectric layer of about 55 Angstromsthick, and an upper electrode of CVD titanium nitride of about 200Angstroms thick.

The ALD Al₂O₃ dielectric layer of the first Al₂O₃ MIS capacitor wasformed by atomic layer deposition using trimetyl-aluminum (TMA) as analuminum source precursor and water. The titanium nitride upperelectrode was formed by chemical vapor deposition, employing TiCl₄(titanium tetrachloride) as precursor and ammonia (NH₃) as nitrogensource.

A third group of measurements for the capacitance and leakage current ofthe first Al₂O₃ MIS capacitor described above was conducted from variousdie locations across the wafer. The capacitance measurements wereconducted at 1 kHz and zero (0) bias, and the corresponding leakagecurrent measurements were conducted at 1.5 V DC bias and at about 85° C.The distribution of the leakage current vs. capacitance measurements forthe first Al₂O₃ MIS capacitor was recorded as region C in FIG. 20. Asillustrated in FIG. 20, for capacitance values of about 31 to 35 fF/cellcorresponding to the region C, the leakage current values are within 0.4to 2.0 fA/cell.

Fourth Set of Experiments

Under a fourth set of experiments, a second Al₂O₃ MIS capacitor wasformed on a semiconductor wafer according to a second embodiment of thepresent invention. The second Al₂O₃ MIS capacitor was fabricated with alower electrode of CVD deposited hemispherical grained polysilicon ofabout 400 Angstroms thick, an ALD Al₂O₃ dielectric layer of about 55Angstroms thick subjected to a post-Al₂O₃ deposition treatment, and anupper electrode of CVD titanium nitride of about 200 Angstroms thick.

The ALD Al₂O₃ dielectric layer of the second Al₂O₃ MIS capacitor wasformed by atomic layer deposition using trimetyl-aluminum (TMA) as analuminum source precursor and water. The titanium nitride upperelectrode was formed by chemical vapor deposition, employing TiCl₄(titanium tetrachloride) as precursor and ammonia (NH₃) as a nitrogensource.

Prior to the formation of the ALD Al₂O₃ dielectric layer, the lower HSGelectrode of the second Al₂O₃ MIS capacitor was subjected to thefollowing sequence of treatments: (1) a dilute hydrofluoric acid (HF)solution having a 10:1 volumetric ratio of water to 49% HF; (2) anin-situ PH₃ anneal at about 750° C. and for about 30 minutes; (3) adilute hydrofluoric acid (HF) solution having a 10:1 volumetric ratio ofwater to 49% HF; and (4) an RTN treatment at about 800° C. for about 60seconds in a nitrogen atmosphere.

A fourth group of measurements for the capacitance and leakage currentof the second Al₂O₃ MIS capacitor described above was conducted fromvarious die locations across the wafer. The capacitance measurementswere conducted at 1 kHz and zero (0) bias, and the corresponding leakagecurrent measurements were conducted at 1.5 V DC bias and at about 85° C.The distribution of the leakage current vs. capacitance measurements forthe second Al₂O₃ MIS capacitor was recorded as region D in FIG. 20. Forcapacitance values of about 35 to 38 fF/cell corresponding to the regionD of FIG. 20, the leakage current values are within 0.5 to 3.0 fA/cell.

Fifth Set of Experiments

Under a fifth set of experiments, a third Al₂O₃ MIS capacitor was formedon a semiconductor wafer according to a third embodiment of the presentinvention. The third Al₂O₃ MIS capacitor was fabricated with a lowerelectrode of CVD deposited hemispherical grained polysilicon of about400 Angstroms thick, an ALD Al₂O₃ dielectric layer of about 50 Angstromsthick and subjected to a reoxidation treatment, and an upper electrodeof CVD titanium nitride of about 200 Angstroms thick.

The ALD Al₂O₃ dielectric layer of the third Al₂O₃ MIS capacitor wasformed by atomic layer deposition using trimethyl-aluminum (TMA) as analuminum source precursor and water. Subsequent to its formation, theALD Al₂O₃ dielectric layer of the third Al₂O₃ MIS capacitor wassubjected to a post-deposition oxidation treatment. This way, the ALDAl₂O₃ dielectric layer underwent an oxidizing ambient under an ozonetreatment at about 475° C. for about 3 minutes. The titanium nitrideupper electrode was formed by chemical vapor deposition, employing TiCl₄as precursor and ammonia (NH₃) as a nitrogen source.

A fifth group of measurements for the capacitance and leakage current ofthe third Al₂O₃ MIS capacitor described above was conducted from variousdie locations across the wafer. The capacitance measurements wereconducted at 1 kHz and zero (0) bias, and the corresponding leakagecurrent measurements were conducted at 1.5 V DC bias and at about 85° C.The distribution of the leakage current vs. capacitance measurements forthe third Al₂O₃ MIS capacitor was recorded as region E in FIG. 20. Asillustrated in FIG. 20, for capacitance values of about 20 to 24 fF/cellcorresponding to the region E, the leakage current values are within 0.1to 0.4 fA/cell.

The results of the five sets of experiments detailed above demonstratethat the leakage current of an MIS capacitor fabricated according tovarious embodiments of the present invention is substantially decreasedwhen the ALD Al₂O₃ dielectric layer is subjected to a reoxidationtreatment, such as the ozone reoxidation at about 475° C. for about 3minutes explained above with reference to the fifth group ofmeasurements. This is exemplified by region E of FIG. 20, according towhich the leakage current values for the third Al₂O₃ MIS capacitor fallbetween 0.1 to 0.4 fA/cell. However, the capacitance valuescorresponding to region E of FIG. 20 are also unacceptably low comparedto the capacitance values of the other four capacitors and theircorresponding regions A, B, C and D of FIG. 20.

The results of the five sets of experiments also demonstrate thatsubjecting the HSG lower electrode to a PH₃ anneal and an RTN treatmentbefore the formation of the ALD Al₂O₃ dielectric layer substantiallyincreases the capacitance values. FIG. 20 shows that the highestcapacitance values among all MIS capacitors correspond to region D ofthe second Al₂O₃ MIS capacitor. The capacitance values of the secondAl₂O₃ MIS capacitor, which fall between 35 to 38 fF/cell (region D ofFIG. 20), are higher than the capacitance values of all other fourregions A, B, C, and E corresponding to the other four capacitors.

Although the exemplary embodiments of the present invention have beendescribed with reference to the formation of one MIS capacitor 100 (FIG.18), the invention also contemplates the formation of a plurality ofsuch capacitors, as desired in a DRAM memory array. In addition, theinvention contemplates the fabrication of an MIS capacitor, such as theMIS capacitor 100 of FIG. 18, on an integrated circuit substrate whichmay include other capacitor structures, for example, conventionalcontainer capacitors, MIM or SIS capacitors, among others.

In addition, although the formation of the MIS capacitor 100 (FIG. 18)has been described with reference to the formation of the uppercapacitor electrode 90 formed over the Al₂O₃ dielectric layer 70 (FIG.12), the invention also contemplates the formation of an MIS capacitorcomprising an upper capacitor electrode formed over the Al₂O₃ compositestack layer 80 (FIG. 16), which as described above may be, for example,an in-situ deposited composite stack of Al₂O₃/Ta₂O₅/Al₂O₃ (aluminumoxide/tantalum oxide/aluminum oxide), or over the Al₂O₃ dielectric layer70 with at least one of the interfacial layers 72, 74 (FIGS. 13–15).Further, although Al₂O₃ (aluminum oxide) is the preferred dielectricmaterial for the dielectric layer 70 (FIG. 12), the invention is notlimited to aluminum oxide. Accordingly, the invention also contemplatesthe use of other dielectric materials which can form stable compositestacks with other oxide dielectric materials, such as tantalum oxide,(Ta₂O₅), zirconium oxide (ZrO₂), hafnium oxide (HfO), ahafnium-aluminum-oxygen alloy (Hf—Al—O), or a lanthanum-aluminum-oxygenalloy (La—Al—O), among others. The invention further contemplates theuse of dielectric materials which are oxides and/or oxide combinationsof scandium (Sc), yttrium (Y), lanthanum (La), titanium (Ti), zirconium(Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta) andtungsten (W).

Accordingly, the above description and drawings are only to beconsidered illustrative of exemplary embodiments which achieve thefeatures and advantages of the present invention. Modification andsubstitutions to specific process conditions and structures can be madewithout departing from the spirit and scope of the present invention.Thus, the invention is not to be considered as being limited by theforegoing description and drawings, but is only limited by the scope ofthe appended claims.

1. A method of forming an MIS capacitor on a semiconductor substrate,comprising the acts of: forming a semiconductive layer of hemisphericalgrained polysilicon over a substrate; opening the grains which form saidlayer of hemispherical grained polysilicon to activate said grains;forming a dielectric layer comprising aluminum oxide over saidsemiconductive layer by atomic layer deposition; and forming a metalnitride layer over said dielectric layer.
 2. The method of claim 1,wherein said act of opening said grains further comprising etching saidlayer of hemispherical grained polysilicon to form an etched layer ofhemispherical grained polysilicon.
 3. The method of claim 2, whereinsaid act of etching said layer of hemispherical grained polysiliconfurther comprises contacting said layer of hemispherical grainedpolysilicon with a solution of HF.
 4. The method of claim 3 furthercomprising the act of subjecting said layer of hemispherical grainedpolysilicon to an RTN process.
 5. The method of claim 3 furthercomprising the act of subjecting said layer of hemispherical grainedpolysilicon to an anneal process.
 6. The method of claim 3 furthercomprising the act of subjecting said layer of hemispherical grainedpolysilicon to a PH₃ anneal.
 7. The method of claim 1, wherein saidmetal nitride layer is a titanium nitride layer formed by CVD.
 8. Themethod of claim 1, wherein said metal nitride layer is a titaniumnitride layer formed by ALD.
 9. The method of claim 8, wherein saidtitanium nitride layer is formed by ALD using a nitrogen source and atitanium source precursor.
 10. The method of claim 1, wherein said metalnitride layer is a tungsten nitride layer formed by CVD.
 11. The methodof claim 1, wherein said metal nitride layer is a tungsten nitride layerformed by ALD.
 12. The method of claim 1, wherein said metal nitridelayer is a boron-doped tungsten nitride layer formed by CVD.
 13. Themethod of claim 12, wherein said act of providing said boron-dopedtungsten nitride layer further comprises the act of incorporating boroninto a tungsten nitride layer.
 14. The method of claim 1, wherein saidaluminum oxide dielectric layer is formed by ALD using an ozone sourceand an aluminum source precursor.
 15. The method of claim 14, whereinsaid aluminum source precursor is trimethyl-aluminum.
 16. The method ofclaim 1, wherein said aluminum oxide dielectric layer is formed to athickness of about 10 Angstroms to about 500 Angstroms.
 17. The methodof claim 16, wherein said aluminum oxide dielectric layer is formed to athickness of about 25 Angstroms to about 100 Angstroms.
 18. The methodof claim 1, wherein said aluminum oxide dielectric layer furthercomprises a material selected from the group consisting of tantalumoxide, zirconium oxide, hafnium oxide, hafnium-aluminum-oxygen alloysand lanthanum-aluminum-oxygen alloys.
 19. The method of claim 18,wherein said aluminum oxide dielectric layer is formed as a compositestack of at least one aluminum oxide layer and at least one tantalumoxide layer.
 20. The method of claim 19, wherein said aluminum oxidedielectric layer is formed of interleaved layers of aluminum oxide andtantalum oxide.
 21. The method of claim 20, wherein said aluminum oxidedielectric layer is an aluminum oxide/tantalum oxide/aluminum oxidestack.
 22. A method of forming an MIS capacitor on a semiconductorsubstrate, comprising the acts of: forming a semiconductive layer ofhemispherical grained polysilicon over a substrate; opening the grainswhich form said layer of hemispherical grained polysilicon to activatesaid grains; forming a dielectric layer comprising aluminum oxide oversaid semiconductive layer by atomic layer deposition; and forming ametal nitride layer over said dielectric layer, wherein said metalnitride layer is a boron-doped titanium nitride layer formed by CVD. 23.The method of claim 22, wherein said act of providing said boron-dopedtitanium nitride layer further comprises the act of incorporating boroninto a titanium nitride layer.
 24. The method of claim 23, wherein saidact of incorporating boron into a titanium nitride layer furthercomprises the act of exposing said titanium nitride layer to B₂H₆. 25.The method of claim 24, wherein said act of incorporating boron into atitanium nitride layer further comprises the act of exposing saidtitanium nitride layer to B₂H₆ at a temperature of about 200° C. toabout 600° C.
 26. A method of forming an aluminum oxide MIS capacitor ona semiconductor substrate, comprising the acts of: forming a lowercapacitor electrode of hemispherical grained polysilicon over saidsemiconductor substrate; forming a dielectric composite stack comprisingaluminum oxide over said lower capacitor electrode; and forming an uppercapacitor electrode of tungsten nitride over said dielectric compositestack.
 27. The method of claim 26, wherein said dielectric compositestack is formed by ALD.
 28. The method of claim 27, wherein saiddielectric composite stack is formed of interleaved layers of aluminumoxide and another metal oxide material.
 29. The method of claim 28,wherein said metal oxide material is selected from the group consistingof tantalum oxide, zirconium oxide, hafnium oxide,hafnium-aluminum-oxygen alloys and lanthanum-aluminum-oxygen alloys. 30.The method of claim 26 further comprising the act of subjecting saiddielectric composite stack to a nitridizing treatment.
 31. The method ofclaim 30 further comprising the act of subjecting said dielectriccomposite stack to a PH₃ anneal treatment.
 32. The method of claim 26,wherein said tungsten nitride layer is formed by ALD using a tungstensource and a nitrogen source precursor.
 33. The method of claim 26further comprising the act of etching said hemispherical grainedpolysilicon to form an etched hemispherical grained polysilicon.
 34. Themethod of claim 33, wherein said act of etching said hemisphericalgrained polysilicon further comprises contacting said hemisphericalgrained polysilicon with a solution of HF.
 35. The method of claim 34further comprising the act of subjecting said hemispherical grainedpolysilicon to a PH₃ anneal.
 36. The method of claim 35 furthercomprising the act of subjecting said hemispherical grained polysiliconto an RTN treatment.
 37. The method of claim 36 further comprising theact of subjecting said hemispherical grained polysilicon to a HFsolution after said PH₃ anneal and before said RTN treatment.